Processes for dyeing of keratinous fibers with compositions which contain 2-sulfurated metaphenylenediamines in combination with oxidation dye precursors

ABSTRACT

Processes for dyeing keratinous fibers with compositions which contain at least one 2-sulphured metaphenylenediamine of formula (I) ##STR1## wherein Z is alkyl, aralkyl, monohydroxyalkyl, polyhydroxyalkyl, aryl or aminoalkyl; R 1  and R 2 , which are the same or different, are hydrogen, alkyl, monohydroxyalkyl, polyhydroxyalkyl, monocarbamylalkyl, dialkylcarbamyl, aminoalkyl, acyl carbalkoxy, carbamyl, or monoalkylcarbamyl; R 3  is hydrogen, alkyl, nitrile, amide, fluoroalkyl, or --COOR; and the corresponding acid salts, and at least one oxidation dye precursor.

The present invention relates to the use for dyeing keratinous fibers and more particularly human hair of 2-sulfurated metaphenylenediamines, to dyeing compositions containing these 2-sulfurated metaphenylenediamines, to a dyeing process using these compositions and to novel sulfurated metaphenylenediamines and their process of preparation.

Sulfurated derivatives of aromatic amines, in combination with oxidation dye precursors, have already been used for dyeing keratinous fibers.

It is known to dye keratinous fibers and in particular human hair with dyeing compositions containing oxidation dye precursors and couplers.

The couplers, also called the coloring modifiers, make it possible to vary the shades obtained with the oxidation dye precursors.

In the field of dyeing keratinous fibers and in particular human hair, the search is for couplers which, in combination with oxidation dye precursors, make it possible to obtain a wide range of shades, while conferring on hair a coloring having a satisfactory resistance to light, to washing, to bad weather, to perspiration and to the various treatments which hair may be subjected to.

The applicants have discovered, which forms the subject of the invention, that the use of certain 2-sulfurated metaphenylenediamines as couplers with oxidation dye precursors of ortho and/or para type in dyeing compositions for keratinous fibers made it possible to obtain, on application to keratinous fibers and in particular human hair, a wide range of coloring shades exhibiting a particularly outstanding resistance to light, to washing, to bad weather, to perspiration and to the various treatments which hair may be subjected to.

The invention applies to the use of these 2-sulfurated metaphenylenediamines for dyeing keratinous fibers and in particular human hair.

Another subject of the invention consists of oxidation dyeing compositions, intended to be used for dyeing keratinous fibers and in particular human hair, containing at least one oxidation dye precursor of ortho and/or para type and at least certain 2-sulfurated metaphenylenediamines.

The invention also applies to the process for coloring keratinous fibers and in particular human hair using such a composition mixed with an oxidizing agent.

Another subject of the invention is novel 2-sulfurated metaphenylenediamines and their process of preparation.

Other subjects of the invention will become apparent on reading the description and examples which follow.

The subject of the present invention is thus the use, for dyeing keratinous fibers and in particular human hair, of at least one 2-sulfurated metaphenylenediamine of general formula: ##STR2## in which: Z represents a C₁ -C₁₈ alkyl radical, an aralkyl radical in which the alkyl radical is C₁ -C₆, a C₁ -C₆ monohydroxyalkyl or C₂ -C₆ polyhydroxyalkyl radical, an aryl radical or an aminoalkyl radical of formula: ##STR3## in which n is an integer between 1 and 6 inclusive and R₄ and R₅, which are identical or different, represent a hydrogen atom or a C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl or C₁ -C₆ acyl radical;

R₁ and R₂, which are identical or different, represent a hydrogen atom, a C₁ -C₆ alkyl radical, a C₁ -C₆ monohydroxyalkyl radical, a C₂ -C₆ polyhydroxyalkyl radical, a C₁ -C₆ monocarbamoylalkyl radical, a C₁ -C₆ dialkylcarbamoyl radical, a C₁ -C₆ aminoalkyl radical, a C₁ -C₆ acyl radical, a C₂ -C₆ carbalkoxy radical, a carbamoyl radical or a C₁ -C₆ monoalkylcarbamoyl radical;

R₃ represents a hydrogen atom, a C₁ -C₄ alkyl radical, a nitrile radical, an amide radical, a C₁ -C₄ fluoroalkyl radical or a radical --COOR where R represents a hydrogen atom or a C₁ -C₄ alkyl radical, and the acid salts corresponding to the compounds of formula (I).

Among the preferred meanings of the Z radical in the sulfurated metaphenylenediamines of general formula (I) according to the invention, the C₁ -C₁₈ alkyl radical denotes the methyl, ethyl, propyl, butyl, dodecyl or hexadecyl radicals; the aralkyl radical denotes the benzyl radical; the mono- or polyhydroxyalkyl radical denotes --CH₂ --CH₂ OH, --CH₂ --CHOH--CH₂ --OH or --CH₂ --CHOH--CH₃ ; the aryl radical denotes phenyl; the aminoalkyl radical denotes ##STR4## when the R₁, R₂, R₄ and R₅ groups represent an acyl radical, the latter preferably denotes the formyl, acetyl and propionyl radicals.

When the R₃ group denotes an alkyl radical, the latter is a methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl radical. Among the fluoroalkyl radicals, mention may be made of trifluoromethyl and trifluoroethyl.

The acid salts corresponding to the sulfurated metaphenylenediamine compounds of general formula (I) are preferably chosen from the hydrochlorides, sulfates or hydrobromides.

Mention may be made, among the sulfurated metaphenylenediamines of general formula (I), of:

2-β-acetylaminoethylthio-1,3-diaminobenzene,

2-methylthio-5-methyl-1,3-diaminobenzene,

2-methylthio-5-amido-1,3-diaminobenzene,

2-methylthio-5-nitrilo-1,3-diaminobenzene,

2-methylthio-5-trifluoromethyl-1,3-diaminobenzene,

2-methylthio-1,3-diaminobenzene,

2-methylthio-3-amino-1-(carbamoyl-t-butyl)benzene,

2-methylthio-1,3-di (carbamoyl-t-butyl)benzene,

2-methylthio-1,3-diacetylaminobenzene,

2-n-propylthio-5-trifluoromethyl-1,3-diaminobenzene,

2-isopropylthio-5-trifluoromethyl-1,3-diaminobenzene,

2-methylthio-4-methyl-1,3-diaminobenzene,

2-ethylthio-5-trifluoromethyl-1,3-diaminobenzene,

2-isobutylthio-5-trifluoromethyl-1,3-diaminobenzene,

2-n-butylthio-5-trifluoromethyl-1,3-diaminobenzene, and their acid salts.

The more particularly preferred compounds are:

2-β-acetylaminoethylthio-1,3-diaminobenzene,

2-methylthio-5-methyl-1,3-diaminobenzene,

2-methylthio-5-amido-1,3-diaminobenzene,

2-methylthio-5-nitrilo-1,3-diaminobenzene,

2-methylthio-5-trifluoromethyl-1,3-diaminobenzene,

2-methylthio-1,3-diaminobenzene and their acid salts.

The compounds of formula (I) can be used as couplers in the presence of oxidation dye precursors of ortho and/or para type known in themselves making it possible to dye hair by oxidation coloring according to a process using an oxidative condensation reaction of the precursors and of the coupler.

The dye precursors of ortho and/or para type are compounds which are not dyes in themselves but which form a dye by an oxidative condensation process either with themselves or in the presence of a coupler or modifier.

These oxidation dye precursors of ortho or para type are benzene or heterocyclic compounds which contain two functional groups, amino or hydroxyl and emino, in positions ortho or para with respect to one another.

Oxidation dye precursors of ortho or para type can be chosen from paraphenylenediamines, paraaminophenols, para heterocyclic precursors derived from pyridine or pyrimidine, such as 2,5-diaminopyridine, 2-hydroxy-5-aminopyridine, 2,4,5,6-tetraaminopyrimidine, 4,5-diamino-1-methylpyrazole or 2-dimethylamino-4,5,6-triaminopyrimidine, orthoaminophenols and the so-called "double" bases.

As paraphenylenediamines, there may more particularly be mentioned the compounds corresponding to the formula (III): ##STR5## in which: R₆, R₇ and R₈, which are identical or different, represent a hydrogen or halogen atom, an alkyl radical, an alkoxy radical or a C₁ -C₄ hydroxyalkyl, sulfo or carboxyl radical;

R₉ and R₁₀, which are identical or different, represent a hydrogen atom or an alkyl, hydroxyalkyl, alkoxyalkyl, carbamoylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl, carbalkoxyaminoalkyl, sulfoalkyl, piperidinoalkyl, morpholinoalkyl or phenyl radical, the phenyl radical optionally being substituted in the para position by an amino group; or else R₉ and R₁₀ form, jointly with the nitrogen atom to which they are bonded, a piperidino or morpholino heterocycle, with the proviso that R₆ or R₈ represents a hydrogen atom when R₉ and R₁₀ do not represent a hydrogen atom, and the salts of these compounds. These alkyl or alkoxy radicals preferably have 1 to 4 carbon atoms and denote especially methyl, ethyl, propyl, methoxy and ethoxy radicals.

Among compounds of formula (III), mention may more particularly be made of paraphenylenediamine, p-toluylenediamine, methoxyparaphenylenediamine, chloroparaphenylenediamine, 2,3-dimethylparaphenylenediamine, 2,6-dimethylparaphenylenediamine, 2,6-diethylparaphenylenediamine, 2,5-dimethylparaphenylenediamine, 2-methyl-5-methoxyparaphenylenediamine, 2,6-dimethyl-5-methoxyparaphenylenediamine, N,N-dimethylparaphenylenediamine, N,N-diethylparaphenylenediamine, N,N-dipropylparaphenylenealiamine, 3-methyl-4-amino-N,N-diethylaniline, N,N-di(β-hydroxyethyl)paraphenylenediamine, 3-methyl-4-amino-N,N-di(β-hydroxyethyl)aniline, 3-chloro-4-amino-N,N-di(β-hydroxyethyl)aniline, 4-amino-N,N-(ethyl, carbamoylmethyl)aniline, 3-methyl-4-amino-N,N-(ethyl, carbamoylmethyl)aniline, 4-amino-N,N-(ethyl,(β-piperidinoethyl)aniline, 3-methyl-4-amino-N,N-(ethyl,β-piperidinoethyl)aniline, 4-amino-N,N-(ethyl,β-morpholinoethyl)aniline, 3-methyl-4-amino-N,N-(ethyl,β-morpholinoethyl)aniline, 4-amino-N,N-(ethyl,β-acetylaminoethyl)aniline, 4-amino-N-(β-methoxyethyl)aniline, 3-methyl-4-amino-N,N-(ethyl, β-acetylaminoethyl)aniline, 4-amino-N,N-(ethyl, β-mesylaminoethyl)aniline, 3-methyl-4-amino-N,N-(ethyl, β-mesylaminoethyl)aniline, 4-amino-N,N-(ethyl, β-sulfoethyl)aniline, 3-methyl-4-amino-N,N-(ethyl, β-sulfoethyl)aniline, N-[(4'-amino)phenyl]morpholine, N-[(4'-amino)phenyl]piperidine, 2-hydroxyethylparaphenylenediamine, fluoroparaphenylenediamine, carboxyparaphenylenediamine, sulfoparaphenylenediamine, 2-isopropylparaphenylenediamine, 2-n-propylparahenylenediamine, hydroxy-2-(n-propyl)paraphenylenediamine, 2-hydroxymethylparaphenylenediamine, N,N-dimethyl -3-methylparaphenylenediamine, N,N-(ethyl, β-hydroxyethyl)paraphenylenediamine, N-(dihydroxypropyl) paraphenylenediamine, N-4'- aminophenylparaphenylenediamine or N-phenylparaphenylenediamine.

These paraphenylenediamines can be used either in the free base form or in the form of salts, such as hydrochloride, hydrobromide or sulfate.

Among the p-aminophenols, mention may be made of p-aminophenol, 2-methyl-4-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol, 2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4-aminophenol, 2,3-dimethyl-4-aminophenol, 2,5-dimethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-(β-hydroxyethyl)4-aminophenol, 2-methoxy-4-aminophenol, 3-methoxy-4-aminophenol, 3-(β-hydroxyethoxy)4-aminophenol, 2-methoxymethyl-4-aminophenol, 2-aminomethyl-4-aminophenol, 2-(β-hydroxyethylaminomethyl)-4-aminophenol, 2-ethoxymethyl-4-aminophenol or 2-[(β-hydroxyethoxy)methyl]-4-aminophenol.

The so-called "double" bases are bisphenylalkylenediamines, corresponding to the formula: ##STR6## in which: Z₁ and Z₂, which are identical or different, represent hydroxyl groups or groups NHR₁₅ where R₁₅ denotes a hydrogen atom or a lower alkyl radicals

R₁₂ and R₁₃, which are identical or different, represent either hydrogen atoms, or halogen atoms, or also alkyl radicals;

R₁₁ and R₁₄, which are identical or different, represent a hydrogen atom or an alkyl, hydroxyalkyl or aminoalkyl radical, it being possible for the amino residue to be substituted;

Y represents a radical taken from the group consisting of the following radicals: ##STR7## in which n is an integer between 0 and 8 and m, q and p are integers between 0 and 4, it also being possible for this base to be provided in the form of its addition salts with acids.

The alkyl or alkoxy radicals shown above preferably denote a group having 1 to 4 carbon atoms and especially methyl, ethyl, propyl, methoxy and ethoxy.

Among the compounds of formula (IV), there may be mentioned N,N'-bis(β-hydroethyl)N,N'-bis(4'-aminophenyl)-1,3-diamino-2-propanol, N,N'-bis(β-hydroxyethyl)N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl) tetramethylenediamine, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(4-methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine.

Among the ortho-aminophenols, mention may more particularly be made of 1- amino-2-hydroxybenzene, 6-methyl -1-hydroxy-2-aminobenzene, 4-methyl-1-amino-2-hydroxybenzene or 4-acetylamino-1-amino-2-hydroxybenzene.

The compounds of formula (I) are applied to keratinous fibers and in particular human hair by means of dyeing compositions which constitute another subject of the invention.

The compositions in accordance with the invention contain, in a suitable medium for dyeing, at least one 2-sulfurated metaphenylenediamine defined above. The preferred compositions contain at least one 2-sulfurated metaphenylenediamine defined above in combination with at least one oxidation dye precursor as defined above.

The dyeing compositions in accordance with the invention can also contain, in addition to the coupler corresponding to the formula (I) defined above, other couplers known in themselves, such as metadiphenols, metaaminophenols, metaphenylenediamines other than those of formula (I) above, metaacylaminophenols, metaureidophenols, metacarbalkoxyaminophenols, α-naphthol, indole derivatives or couplers having an active methylene group, such as β-keto compounds or pyrazolones.

Among these couplers, there may be more particularly mentioned 2,4-dihydroxyphenoxyethanol, 2,4-dihydroxyanisole, metaaminophenol, resorcinol monomethyl ether, resorcinol, 2-methylresorcinol, 2-methyl-5-aminophenol, 2-methyl-5-N-(β-hydroxyethyl)aminophenol, 2-methyl-5-N-(β-mesylaminoethyl)aminophenol, 2,6-dimethyl-3-aminophenol, 6-hydroxybenzomorpholine, 2,4-diaminoanisole, 2,4-diaminophenoxyethanol, 6-aminobenzomorpholine, [2-N-(β-hydroxyethyl)amino-4-amino]phenoxyethanol, 2-amino-4-N-(β-hydroxyethyl)aminoanisole, (2,4-diamino)phenyl-β-γ-dihydroxypropyl ether, 2,4-diaminophenoxyethylamine, 1,3-dimethoxy-2,4-diaminobenzene, 1,3,5-trimethoxy-2,4-diaminobenzene, 1-amino-3,4-methylenedioxybenzene, 1-hydroxy-3,4-methylenedioxybenzene, 2-chloro-6-methyl-3-aminophenol, 2-methyl-3-aminophenol, 2-chlororesorcinol, 6-methoxy-3-hydroxyethylaminoaniline, 1-ethoxy-2-bis(β-hydroxyethyl)amino-4-aminobenzene, 3-diethylaminophenol, 1,3-dihydroxy-2-methylbenzene, 1-hydroxy-2,4-dichloro-3-aminobenzene, 4,6-hydroxyethoxy-1,3-diaminobenzene, 4-methyl-6-ethoxy-1,3-diaminobenzene, 4-chloro-6-methyl-3-aminophenol, 6-chloro-3-trifluoroethylaminophenol and their salts.

There may be added to these compositions, as is well known in the state of the art, especially for the purpose of shading or enriching in highlights the colorings introduced by the oxidation dye precursors, direct dyes such as azo dyes, anthraquinone dyes or nitrated derivatives of the benzene series.

The combined oxidation dye precursors of para and/or ortho type, as well as the couplers used in the dyeing compositions in accordance with the invention, preferably represent from 0.3 to 7% by weight with respect to the weight of the said composition. The concentration of sulfurated metaphenylenediamine compounds of formula (I) can vary between 0.05 and 3.5% by weight of the total weight of the composition.

The dyeing compositions in accordance with the invention also contain, in their preferred embodiment, anionic, cationic, nonionic or amphoteric surface-active agents or their mixtures. Among these surface-active agents, there may be mentioned alkylbenzenesulfonates, alkylnaphthalenesulfonates, sulfates, ethersulfates and fatty alcohol sulfonates, quaternary ammonium salts such as trimethylcetylammoniumbromide or cetylpyridinium bromide, optionally oxyethylenated fatty acid ethanolamides, polyglycerolated fatty alcohols, polyoxyethylenated or polyglycerolated alkylphenols, and polyoxyethylenated alkylsulfates .

These surface-active agents are present in the compositions in accordance with the invention in proportions between 0.5 and 55% by weight, and preferably between 2 and 50% by weight, with respect to the total weight of the composition.

These compositions can also contain organic solvents for solubilizing the components which would not be sufficiently soluble in water. Among these solvents, there may be mentioned, by way of example, C₁ -C₄ lower alkanols, such as ethanol and isopropanol; glycerol; glycols or glycol ethers such as 2-butoxyethanol, ethylene glycol, propylene glycol or the monoethyl ether and the monomethyl ether of diethylene glycol, and aromatic alcohols such as benzyl alcohol or phenoxyethanol, the analogous products and their mixtures.

The solvents are preferably present in proportions of between 1 and 40% by weight, and in particular between 5 and 30% by weight, with respect to the total weight of the composition.

The thickening agent which it is possible to add to the compositions in accordance with the invention can be chosen from sodium alginate, gum arabic, optionally crosslinked acrylic acid polymers, cellulose derivatives, or heterobiopolysaccharides, such as xanthan gum. It is also possible to use inorganic thickening agents such as bentonite.

These thickening agents are preferably present in proportions of between 0.1 and 5%, and in particular between 0.2 and 3%, by weight with respect to the total weight of the composition.

The antioxidizing agents which can be present in the compositions are chosen in particular from sodium sulfite, thioglycolic acid, sodium bisulfite, dehydroascorbic acid, hydroquinone and homogentisic acid. These antioxidizing agents are present in the composition in proportions of between 0.05 and 1.5% by weight with respect to the total weight of the composition.

The pH of these compositions is between 4 and 11. It is adjusted to the desired value using basifying agents well known in the state of the art, such as aqueous ammonia, alkali metal carbonates, alkanolamines such as mono-, di-and triethanolamines and their derivatives or sodium and potassium hydroxides, or conventional acidifying agents, such as inorganic or organic acids, such as hydrochloric, tartaric, citric, phosporic and sulfonic acid.

These compositions can also contain other cosmetically acceptable adjuvants, such as, for example, penetration agents, sequestering agents, fragrances, buffers, and the like.

The compositions in accordance with the invention can be provided in various forms, such as in the liquid, cream or gel form or any other form suitable for carrying out dyeing of keratinous fibers and especially of human hair. These compositions can be packaged in aerosol containers in the presence of a propellant and can form foams.

The compounds of formula (I) are used in accordance with the invention according to a process comprising the application to keratinous fibers of the compound of formula (I) and of ortho and/or para oxidation dye precursors in the presence of an oxidizing agent.

The dyeing compositions in accordance with the invention containing an oxidation dye precursor of the para and/or ortho type and a coupler of formula (I) are used according to a process in which development is implemented by an oxidizing agent.

In accordance with this process, the dyeing composition described above is mixed, at the time of use, with an oxidizing solution in an amount sufficient to be able to develop a coloring and the mixture obtained is then applied to keratinous fibers and in particular human hair.

The pH of the composition applied to hair preferably varies between 3 and 11. It is adjusted to the desired value using basifying agents well known in the state of the art, such as aqueous ammonia, alkali metal carbonates, alkanolamines such as mono-, di-and triethanolamine and their derivatives, or sodium or potassium hydroxide, or standard acidifying agents, such as inorganic or organic acids, such as hydrochloric, tartaric, citric, phosphoric and sulfonic acids. The oxidizing solution contains, as oxidizing agent, hydrogen peroxide, urea hydrogen peroxide, persalts, such as ammonium persulfate, organic peracids and their salts or alkali metal bromates. A 20 volumes hydrogen peroxide solution is preferably used.

The mixture obtained is applied to hair and is exposed for 10 to 40 minutes, preferably 15 to 30 minutes, after which it is rinsed, washed with shampoo, rinsed again and dried.

The coupler of formula (I) defined above can also be used in a multi-stage process, consisting, in one of the stages, in applying the oxidation dye precursor of ortho and/or para type or their mixture and, in another stage, in applying a dyeing composition containing the coupler of formula (I).

The oxidizing agent can be introduced, just before application, into the composition applied in the second stage or else be applied to the keratinous fibers themselves, in a third stage, the exposure, pH, washing and drying conditions being identical to those indicated above.

Another subject of the invention consists of novel 2-sulfurated metaphenylenediamines which correspond to the formula: ##STR8## in which: Z' represents a C₁ -C₁₈ alkyl radical, an aralkyl radical in which the alkyl radical is C₁ -C₆, a C₁ -C₆ monohydroxyalkyl or C₂ -C₆ polyhydroxyalkyl radical, an aryl radical, an aminoalkyl radical of formula: ##STR9## in which n is an integer between 1 and 6 inclusive; R'₄ and R'₅, which are identical or different, represent a hydrogen atom or a C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl or C₁ -C₆ acyl radical; R'₁ and R'₂, which are identical or different, represent a hydrogen atom, a C₁ -C₆ alkyl radical, a C₁ -C₆ monohydroxyalkyl radical, a C₂ -C₆ polyhydroxyalkyl radical, a C₁ -C₆ monocarbamoylalkyl radical, a C₁ -C₆ dialkylcarbamoyl radical, a C₁ -C₆ aminoalkyl radical, a C₁ -C₆ acyl radical, a C₂ -C₆ carbalkoxy radical, a carbamoyl radical or a C₁ -C₆ monoalkylcarbamoyl radical;

R'₃ represents a hydrogen atom or a C₁ -C₄ alkyl nitrile, amide, C₁ -C₄ fluoroalkyl or --COOR radical where R represents a hydrogen atom or a C₁ -C₄ alkyl radical; and their acid salts, with the proviso that:

when R'₁, R'₂ and R'₃ represent a hydrogen atom, Z' is other than the alkyl radical or the aryl radical;

when Z' represents the methyl radical and R'₃ represents hydrogen, R'₁ and R'₂ cannot both represent the same C₁ -C₆ acyl radical;

when Z' represents the methyl radical and R'₃ represents hydrogen and when one of the two R'₁ and R'₂ radicals represents a hydrogen atom, the other R'₁ or R'₂ radical cannot represent a C₄ acyl radical;

when R'₁ and R'₂ represent hydrogen and R'₃ represents a trifluoromethyl radical in the 5 position, Z cannot represent a C₁ -C₄ alkyl radical;

when R'₁ and R'₂ represent hydrogen and R'₃ represents a methyl radical in the 4 position, Z' cannot denote methyl.

Among compounds corresponding to formula (V) defined above, mention may preferably be made of 2-(β-acetylaminoethylthio)-1,3-diaminobenzene, 2-methylthio-5-methyl-1,3-diaminobenzene, 2-methylthio-5-amido-1,3-diaminobenzene and 2-methylthio-5-nitrilo-1,3-diaminobenzene.

Another subject of the invention is the dyeing compositions of the type defined above containing the compounds of formula (V) and the use of these compounds for dyeing keratinous fibers.

The sulfurated metaphenylenediamines of formula (V) or their salts can be prepared according to a multistage process.

According to a first process and in a first stage, halo-2,6-dinitrobenzene or a substituted derivative is reacted, in the presence of a base such as potassium hydroxide or potassium carbonate, with a thiol of formula (VI):

    Z.sub.1 --SH                                               (VI)

in which Z₁ represents a C₁ -C₁₈ alkyl radical, an aralkyl radical in which the alkyl radical is C₁ -C₆, a C₁ -C₆ monohydroxyalkyl radical, a C₂ -C₆ polyhydroxyalkyl radical, an aryl radical or a group of formula (VII): ##STR10## in which R'₄ and n have the meanings shown above in the formula (V); and

R₁₆ represents a hydrogen atom or a C₁ -C₃ alkyl radical; in a second stage, the nitro substituents of the compound of formula (VIII): ##STR11## obtained previously are reduced to prepare a compound corresponding to the formula (IX): ##STR12## in which Z₁ has the meaning shown above; optionally, in a third stage, and depending on the sulfurated metaphenylenediamine of formula (I) which it is desired to obtain, there is carried out

a) either a monosubstitution of the aromatic amines to obtain a compound of formula (I) in which R'₁ and/or R'₂ are other than H,

b) or an acid hydrolysis of the compound of formula (IX) in which Z₁ represents the group of formula (VII) to obtain the compound of formula (X) ##STR13## in which R'₄ and n have the meanings shown above, R'₄ not, however, denoting C₁ -C₆ acyl radical,

it being possible for the amines attached to the nucleus to then be monosubstituted,

c) or, beforehand, the amine in the compound of formula (IX) which is not attached to the nucleus is substituted to obtain the compound of formula (XI) ##STR14## in which R'₄, R'₅ and n have the meanings shown above, it being possible for the amines which are attached to the nucleus to then be monosubstituted.

According to a second process and in a first stage, a substituted fluoronitrobenzene of formula (XII) ##STR15## in which R₁₇ represents a C₁ -C₆ acyl group and X represents hydrogen, or else R₁₇ and X form, jointly with the nitrogen atom to which they are bonded, an oxazolidone ring, is reacted with a thiol of formula: in which M is an alkali metal and Z₁ has the meanings shown above.

In a second stage, the nitro substituent of the compound of formula (XIV) ##STR16## obtained above is reduced to obtain the compound of formula (XV) ##STR17## in which R₁₇ and X have the meanings shown above; optionally, in a third stage, and depending on the 2-sulfurated metaphenylenediamine of formula (I) which it is desired to obtain, the aromatic amine is monosubstituted to obtain a compound of formula (I) in which R'₁ or R'₂ is other than H.

Finally, in a last stage, the compound is subjected to acid hydrolysis in order to cleave the protective group.

The reduction of the nitro groups is preferably carried out by using iron in acetic medium or else with cyclohexene in the presence of a palladium/charcoal catalyst or by any other standard reduction process.

The substitution of the aromatic amines or of the amine which is not attached to the nucleus can be carried out by reacting with, for example, ethyl bromide, glycol bromohydrin, ethyl-chloroformate, β-chloroacetamide or acetic anhydride.

The examples which follow are intended to illustrate the invention without, however, any limiting nature being implied.

PREPARATION EXAMPLES EXAMPLE 1

Preparation of 2-methylthio-1,3-diaminobenzene dihydrochloride

A solution of 24.3 g (0.12 mol) of 2-chloro-1,3-dinitrobenzene in 60 ml of dimethoxyethane is added dropwise, over 1/2 hour and while maintaining the temperature between 20° and 25° C., to a suspension of 16.8 g (0.24 mol) of sodium thiomethylate in 120 ml of dimethoxyethane. After stirring for 30 minutes at room temperature, the reaction medium (brown suspension) is run into 800 ml of ice-cold water.

The oily precipitate is extracted with ethyl acetate. After treating with Ceca charcoal and with dry sodium sulfate, the ethyl acetate phase is filtered through paper and evaporated to dryness under reduced pressure. An orangey oil (14.8 g) of 2-methylthio-1,3-dinitrobenzene is obtained. This oil is dissolved in 30° ml of 96° ethanol and added dropwise to a suspension, heated to reflux, of 2.9 g of ammonium chloride and 63 g of finely-powdered zinc in 180 ml of alcohol and 26 ml of water.

The reaction is exothermic.

The colorless reaction medium is filtered while boiling. The filtrate is cooled to 0° C. and acidified with 24 ml of an approximately 7N solution of hydrochloric acid in absolute ethanol.

After diluting with 1.5 ml of acetone, the expected dihydrochloride crystallizes.

The white crystals are filtered off, washed with acetone and dried under vacuum, over potassium hydroxide, at 40° C.

There are obtained 7.3 g of the expected dihydrochloride, melting with decomposition at 240°-245° C. and of which the elemental analysis, calculated for C₇ H₁₂ N₂ SCl₂, is

    ______________________________________                                         %         C         H      N      S    Cl                                      ______________________________________                                         Calculated                                                                               37.01     5.32   12.33  14.12                                                                               31.21                                   Found     37.06     5.32   12.35  14.10                                                                               31.33                                   ______________________________________                                    

EXAMPLE 2

Preparation of 2-(β-acetylaminoethylthio)-1,3-diaminobenzene dihydrochloride

1st stage: Synthesis of 2-(β-acetylaminoethylthio)-1,3-dinitrobenzene.

10 g of potassium hydroxide powder are dissolved in a solution of 35.7 g (0.3 mol) of N-(2-mercaptoethyl)acetamide in 100 ml of dimethoxyethane heated to 45° C.

After cooling to 15° C., a solution of 24.3 g (0.12 mol) of 2-chloro-1,3-dinitrobenzene in 50 ml of dimethoxyethane is run in dropwise over 30 min.

The temperature is maintained between 15° and 20° C. for an additional 30 min.

The reaction mixture is poured into 300 ml of ice-cold water.

The orangey-yellow crystalline precipitate is filtered off, reslurried in water and dried under vacuum at 30° C. over phosphorus pentoxide.

After recrystallizing from 96° ethanol, there are obtained 15.7 g of yellow crystals melting at 110° C. and of which the elemental analysis, calculated for C₁₀ H₁₁ N₃ O₅ S, is

    ______________________________________                                         %         C         H      N      O    S                                       ______________________________________                                         Calculated                                                                               42.10     3.89   14.73  28.04                                                                               11.24                                   Found     42.32     3.93   14.68  27.84                                                                               11.18                                   ______________________________________                                    

2nd stage: Reduction

The reduction of the compound obtained above in the 1st stage is carried out according to the procedure described for Example 1.

The dihydrochloride obtained is purified by recrystallization from a water/ethanol (1/6) mixture at reflux.

There are obtained white crystals melting with decomposition at 197°-200° C. and of which the elemental analysis, calculated for C₁₀ H₁₇ N₃ OSCl₂, is:

    ______________________________________                                         %        C      H        N    O      S    Cl                                   ______________________________________                                         Calculated                                                                              40.27  5.75     14.09                                                                               5.36   10.75                                                                               23.78                                Found    40.08  5.80     14.06                                                                               5.85   10.68                                                                               23.60                                ______________________________________                                    

EXAMPLE 3

Preparation of 2-methylthio-5-methyl-1,3-diaminobenzene dihydrochloride

1st stage: Synthesis of 2-methylthio-5-methyl-1,3-dinitrobenzene

A solution of 50.0 g (0,231 mol) of 2-chloro-5-methyl-1,3-dinitrobenzene in 140 ml of dimethoxyethane is added dropwise, over one hour and while maintaining the temperature between 17° C. and 20° C., to a suspension of 25 g (0.35 mol) of sodium thiomethylate in 250 ml of dimethoxyethane.

After stirring for one hour at room temperature, the reaction mixture is run into 1.5 l of ice-cold water.

The crystalline precipitate is filtered off, reslurried in water, dried and then recrystallized from boiling ethyl acetate.

There are obtained 22.2 g of pale-yellow crystals melting at 106° C. and of which the elemental analysis, calculated for C₈ H₈ N₂ O₄ S, is:

    ______________________________________                                         %         C         H      N      O    S                                       ______________________________________                                         Calculated                                                                               42.10     3.53   12.27  28.04                                                                               14.05                                   Found     42.18     3.59   12.18  28.25                                                                               14.11                                   ______________________________________                                    

2nd stage: Reduction

A suspension, heated to reflux, of 4.4 g of ammonium chloride and 82 g of finely-powdered zinc in 280 ml of alcohol and 33 ml of water is treated portionwise, so as to maintain the reflux without heating, with 20.5 g (0.09 mol) of the above dinitro compound obtained in the first stage.

The reaction is exothermic.

The reaction mixture is filtered while boiling, partially evaporated so as to remove the alcohol and extracted with ethyl ether.

After drying over sodium sulfate and filtering, the ether phase is acidified with 30 ml of an approximately 6N solution of hydrochloric acid in absolute ethanol.

The 2-methylthio-5-methyl-1,3-diaminobenzene dihydrochloride precipitate is filtered off and dried over potassium hydroxide.

There are obtained 15.2 g of white crystals recrystallized from an ethanol/water mixture melting with decomposition at 220°-224° C. and of which the elemental analysis, calculated for C₈ H₁₂ N₂ S.2HCl, is:

    ______________________________________                                         %         C         H      N      S    Cl                                      ______________________________________                                         Calculated                                                                               39.84     5.85   11.61  13.29                                                                               29.40                                   Found     39.65     5.89   11.81  13.20                                                                               29.30                                   ______________________________________                                    

EXAMPLE 4

Preparation of 2-methylthio-5-amido-1,3-dieminobenzene dihydrochloride.

1st stage: Synthesis of 2-methylthio-5-amido-1,3-dinitrobenzene

This compound is prepared according to the procedure described for Example 3, Stage 1.

There are obtained, from 24.6 g (0.10 mol) of 2-chloro-5-amido-1,3-dinitrobenzene, 5.8 g of yellow crystals recrystallized from 96° ethanol, melting at 196° C. and of which the elemental analysis, calculated for C₈ H₇ N₃ O₅ S, is:

    ______________________________________                                         %         C         H      N      O    S                                       ______________________________________                                         Calculated                                                                               37.36     2.74   16.34  31.10                                                                               12.47                                   Found     37.55     2.76   16.55  31.27                                                                               12.56                                   ______________________________________                                    

2nd stage: Reduction

The reduction is carried out according to the procedure described for Example 3, Stage 2.

There are obtained, from 12.5 g (0.0486 mol) of the dinitro compound obtained in the first stage, 3.6 g of white crystals, recrystallized from a water/ethanol mixture, of 2-methylthio-5-amido-1,3-diaminobenzene dihydrochloride, melting with decomposition at 230°-232° C. and of which the elemental analysis, calculated for C₈ H₁₁ N₃ OS.2HCl, is:

    ______________________________________                                         %        C      H        N    O      S    Cl                                   ______________________________________                                         Calculated                                                                              35.56  4.85     15.55                                                                               5.92   11.87                                                                               26.24                                Found    35.80  4.82     15.43                                                                               6.19   12.07                                                                               26.36                                ______________________________________                                    

EXAMPLE 5

Preparation of 2-methylthio-5-nitrilo-1,3-diaminobenzene monohydrochloride

1st stage: Synthesis of 2-methylthio-5-nitrilo-1,3-diaminobenzene

This compound is prepared according to the procedure described for Example 3, Stage 1.

There are obtained, from 7.5 g (0,033 mol) of 2-chloro-5-nitrile-1,3-dinitrobenzene, 3.7 g of yellow crystals, recrystallized from isopropyl acetate at reflux, melting at 137° C. and of which the elemental analysis, calculated for C₈ H₅ N₃ O₄ S, is:

    ______________________________________                                         %         C         H      N      O    S                                       ______________________________________                                         Calculated                                                                               40.17     2.11   17.57  26.75                                                                               13.40                                   Found     40.29     2.17   17.59  26.93                                                                               13.45                                   ______________________________________                                    

2nd stage: Reduction

The reduction is carried out according to the process described for Example 3, Stage 2.

There are obtained, from 3.5 g (0.0146 mol) of the dinitro compound obtained in the first stage, after recrystallization from an ethanol/water mixture, 1.3 g of white crystals of 2-methylthio-5-nitrilo-1,3-diaminobenzene monohydrochloride melting with decomposition at 198°-200° C. and of which the elemental analysis, calculated for C₈ H₉ N₃ S.HCl, is:

    ______________________________________                                         %         C         H      N      S    Cl                                      ______________________________________                                         Calculated                                                                               44.55     4.67   19.48  14.86                                                                               16.44                                   Found     44.66     4.76   19.64  15.00                                                                               16.43                                   ______________________________________                                    

    ______________________________________                                         Dyeing at acid pH                                                              ______________________________________                                         Composition A                                                                  Oleyl alcohol polyglycerolated with 2 mol                                                                4.0    g                                             of glycerol                                                                    Oleyl alcohol polygylcerolated with 4 mol                                                                5.69   g AM                                          of glycerol at 78% AM                                                          Oleic acid                3.0    g                                             Oleyl amine containing two mol of ethylene oxide                                                         7.0    g                                             sold under the name Ethomeen 012 by                                            the Company Akzo                                                               Diethylaminopropyl laurylamino succinamate,                                                              3.0    g AM                                          sodium salt at 55% AM                                                          Oleyl alcohol             5.0    g                                             Oleic acid diethanolamide 12.0   g                                             Propylene glycol          3.5    g                                             Ethyl alcohol             7.0    g                                             Dipropylene glycol        0.5    g                                             Monomethyl ether of propylene glycol                                                                     9.0    g                                             Sodium metabisulfite as a 35% aqueous solution                                                           0.455  g                                             Ammonium acetate          0.8    g                                             Antioxidizing agent, sequestering agent q.s.                                   Fragrance, preserving agents q.s.                                              Monoethanolamine q.s. for pH                                                                             9.8                                                  Dyes                      x      g                                             Demineralized water q.s. for                                                                             100.0  g                                             ______________________________________                                    

Composition B

It consists of a 20 volumes hydrogen peroxide solution, the pH of which is adjusted between 1 and 1.5 with orthophosphoric acid.

Dyeing protocol

Composition A is mixed, weight for weight, with Composition B containing hydrogen peroxide. The mixture obtained is applied to permanent wave or non-permanent wave natural gray hair containing 90% white hairs for 30 minutes. The hair is then rinsed, washed with shampoo, then rinsed again and dried.

    __________________________________________________________________________     EXAMPLES         1   2    3     4   5                                          __________________________________________________________________________     Composition A containing:                                                      2-(β-acetylaminoethylthio)-1,3-                                                            0.89 g                                                        diaminobenzene dihydrochloride                                                 2-methylthio-1,3-diaminobenzene                                                                     0.68 g                                                    dihydrochloride                                                                2-methylthio-5-methyl-1,3-                                                                               0.724 g                                              diaminobenzene dihydrochloride                                                 2-methylthio-5-nitrilo-1,3-     0.080 g                                        diaminobenzene [sic] monohydro-                                                chloride                                                                       2-methylthio-5-trifluoromethyl-     0.050 g                                    1,3-diaminobenzene monohydro-                                                  chloride                                                                       2,6-dimethylparaphenylenediamine                                                                0.41 g                                                                             0.41 g                                                    paraphenylenediamine      0.324 g                                                                              0.324 g                                        2,4-diaminophenoxyethanol       0.651 g                                                                            0.675 g                                    dihydrochloride                                                                2,6-dimethylparaphenylenediamine    0.627 g                                    dihydrochloride                                                                Mixture, weight for weight, of A                                                                6.4 6.3  6.4   6.5 6.3                                        and B                                                                          pH of the mixture                                                              Shades obtained                                                                on natural gray hair                                                                            blue     golden    medium                                     containing 90% white hairs                                                                      slightly mahogany  blue                                                        green                                                         on permanent wave natural gray                                                                      midnight   deep                                           hair containing 90% white                                                                           blue       blue-                                          hairs                           black                                          __________________________________________________________________________

    ______________________________________                                         Dyeing at basic pH                                                             Composition C                                                                  ______________________________________                                         ® Octyldodecanol sold under the name                                                               8.0        g                                             Eutanol D by the company Henkel                                              ® Oleic acid        20.0       g                                           ® Monoethanolamine laurylethersulfate sold                                                         3.0        g                                             under the name Sipon LM 35 by the                                              Company Henkel                                                               ® Ethyl alcohol     10.0       g                                           ® Benzyl alcohol    10.0       g                                           ® Cetylstearyl alcohol containing 33 mol of                                                        2.4        g                                             ethylene oxide sold under the                                                  name Simulsol GS by the Company Seppic                                       ® Ethylenediaminetetraacetic acid                                                                  0.2        g                                           ® Aqueous solution containing 60% AM of a                                                          3.7        g                                             cationic polymer having the                                                    following repeating unit:                                                     ##STR18##                                                                     ® Monoethanolamine  7.5        g                                           ® Diethanolamide of linoelic acid sold under                                                       8.0        g                                             the name Comperlan F                                                           by the Company Henkel                                                        ® Aqueous ammonia containing 20% NH.sub.3                                                          10.2       g                                           ® Sodium metabisulfite as a 35% aqueous                                                            1.3        g                                             solution                                                                     ® Hydroquinone      0.15       g                                           ® Dyes              x          g                                           ® Demineralized water                                                                              q.s. for 100.0                                                                            g                                           ______________________________________                                    

Composition D

20 volumes hydrogen peroxide at pH =3.

Dyeing protocol

Composition C is mixed, weight for weight, with Composition D. The mixture obtained is applied to permanent wave or non-permanent wave natural gray hair containing 90% white hairs for 30 min. The hair is then rinsed, washed with shampoo, then rinsed again and dried.

    __________________________________________________________________________     EXAMPLES    6   7   8   9   10   11  12   13                                   __________________________________________________________________________     Composition C                                                                  containing:                                                                    2-(β-acetylaminoethyl-                                                                0.60 g  1.20 g                                                     thio)-1,3-diamino-                                                             benzene dihydro-                                                               chloride                                                                       2-methylthio-1,3-di-                                                                           0.45 g  0.90 g                                                 aminobenzene dihydro-                                                          chloride                                                                       1-phenyl-3-methyl-5-         0.2 g                                                                               0.2 g                                                                              0.2 g                                                                               0.2 g                               pyrazolone                                                                     2-methylthio-5-methyl-      0.965 g                                            1,3-diaminobenzene di-                                                         hydrochloride                                                                  2-methylthio-5-amido-            0.337 g                                       1,3-diaminobenzene                                                             dihydrochloride                                                                2-methylthio-5-tri-                  0.468 g                                   fluoromethyl-1,3-                                                              diaminobenzene mono-                                                           hydrochloride                                                                  2-methylthio-5-nitri-                     0.100 g                              lo-1,3-diaminobenzene                                                          monohydro-                                                                     chloride                                                                       paraphenylenediamine                                                                       0.22 g                                                                             0.22 g           0.216 g  0.216 g                              2-methoxymethyl-4-  0.61 g                                                                             0.61 g                                                 aminophenol                                                                    paraaminophenol             0.436 g  0.327 g                                   2,4-diaminophenoxy-              0.170 g                                       ethanol dihydro-                                                               chloride                                                                       2-methyl-5-N-(β-                 0.05 g                                                                             0.251 g                              hydroxyethyl)-                                                                 aminophenol                                                                    Mixture, weight for                                                                        10.4                                                                               10.2                                                                               10.3                                                                               10.4                                                                               10.4 10.5                                                                               10.3 10.5                                 weight, of C and D                                                             pH of the mixture                                                              Shades obtained:                                                               on natural gray                                                                            blue-   green   golden        pur-                                 hair containing 90%                                                                        green           coppery       plish                                white hairs                               beige                                on permanent wave                                                                              strong  bluish   blue                                                                               slightly                                  natural gray hair                                                                              blue    green        irrides-                                  containing 90%                       cent                                      white hairs                          coppery                                   __________________________________________________________________________ 

We claim:
 1. A keratinous fiber dyeing composition comprising, in a medium suitable for dyeing said keratinous fiber,(i) an ortho oxidation dye precursor, or (ii) a para oxidation precursor, or (iii) a mixture of (i) and (ii), and (iv) as a coupler, at least one 2-sulfurated metaphenylenediamine of the formula ##STR19## wherein Z represents C₁ -C₁₈ alkyl, aralkyl wherein the alkyl moiety is C₁ -C₆, C₁ -C₆ monohydroxyalkyl, C₂ -C₆ polyhydroxyalkyl, aryl or aminoalkyl of the formula ##STR20## wherein n is an integer ranging from 1 to 6, and R₄ and R₅, each independently, represent hydrogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl or C₁ -C₆ acyl, R₁ and R₂, each independently, represent hydrogen, C₁ -C₆ alkyl, C₁ -C₆ monohydroxyalkyl, C₂ -C₆ polyhydroxyalkyl, C₁ -C₆ monocarbamoylalkyl, C₁ -C₆ dialkylcarbamoyl, C₁ -C₆ aminoalkyl, C₁ -C₆ acyl, C₂ -C₆ carbalkoxy, carbamoyl or C₁ -C₆ monoalkylcarbamoyl, R₃ represents hydrogen, C₁ -C₄ alkyl, a nitrile radical, an amide radical, a C₁ -C₄ fluoroalkyl radical, --COOR wherein R represents hydrogen or C₁ -C₄ alkyl, and the acid salts thereof.
 2. The dyeing composition of claim 1 which also contains a coupler selected from the group consisting of a metadiphenol, a metaaminophenol, a metaphenylenediamine other than that of formula (I), a metaacylaminophenol, a metaureidophenol, a metacarbalkoxyaminophenol, α-naphthol, an indole derivative and a coupler having an active methylene group.
 3. The dyeing composition of claim 1 which contains from 0.05 to 3.5 percent by weight of said compound of formula (I) based on the total weight of said composition.
 4. The dyeing composition of claim 1 wherein the combined presence of said (i), (ii), (iii) and (iv) components ranges from 0.3 to 7 percent by weight based on the total weight of said composition.
 5. The dyeing composition of claim 1 which also contains(a) a cationic, anionic, nonionic or amphoteric surface-active agent or a mixture thereof, present in an amount ranging from 0.5 to 55 percent by weight based on the total weight of said composition, (b) an organic solvent present in an amount ranging from 1 to 40 percent by weight based on the total weight of said composition, (c) a direct dye, (d) a thickening agent present in an amount ranging from 0.1 to 5 percent by weight based on the total weight of said composition, and (e) an antioxidizing agent present in an amount ranging from 0.05 to 1.5 percent by weight based on the total weight of said composition.
 6. The dyeing composition of claim 1 in liquid, cream or gel form or packaged in an aerosol container in the presence of a propellant.
 7. The keratinous fiber dyeing composition of claim 1 whereinZ represents methyl, ethyl, propyl, butyl, dodecyl, hexadecyl, benzyl phenyl, a mono- or polyhydroxyalkyl selected from --CH₂ --CH₂ --OH, --CH₂ --CHOH--CH₂ --OH and --CH₂ --CHOH--CH₃, or an aminoalkyl selected from the group consisting of --CH₂ --CH₂ --NH₂, --CH₂ --CH₂ --CH₂ --NHCH₃, ##STR21## and --CH₂ --CH₂ --NHCOCH₃ ; and when R₁, R₂, R₄ or R₅ represent acyl, the said acyl is formyl, acetyl or propionyl.
 8. The keratinous fiber dyeing composition of claim 1 wherein the at least one 2-sulfurated metaphenylenediamine is selected from the group consisting of2-β-acetylaminoethylthio-1,3-diaminobenzene, 2-methylthio-5-methyl-1,3-diaminobenzene, 2-methylthio-5-amido-1,3-diaminobenzene, 2-methylthio-5-nitrilo-1,3-diaminobenzene, 2-methylthio-5-trifluoromethyl-1,3-diaminobenzene, 2-methylthio-1,3-diaminobenzene, 2-methylthio-3-amino-1-(carbamoyl-t-butyl) benzene, 2-methylthio-1,3-di(carbamoyl-t-butyl) benzene, 2-methylthio-1,3-diacetylaminobenzene, 2-n-propylthio-5-trifluoromethyl-1,3-diaminobenzene, 2-isopropylthio-5-trifluoromethyl-1,3-diaminobenzene, 2-methylthio-4-methyl-1,3-diaminobenzene, 2-ethylthio-5-trifluoromethyl-1,3-diaminobenzene, 2-isobutylthio-5-trifluoromethyl-1,3-diaminobenzene, 2-n-butylthio-5-trifluoromethyl-1,3-diaminobenzene, and an acid salt thereof.
 9. The keratinous fiber dyeing composition of claim 1 wherein the said salt of the at least one 2-sulfurated metaphenylenediamine is a hydrochloride, a sulfate or a hydrobromide.
 10. The keratinous fiber dyeing composition of claim 1 wherein said oxidation dye precursor is selected from the group consisting of a paraphenylenediamine, a paraaminophenol, a para heterocyclic precursor derived from pyridine or pyrimidine, an ortho aminophenol and abisphenylalkylenediamine.
 11. An oxidant dyeing process of keratinous fibers comprisingapplying to said keratinous fibers a composition comprising(i) an ortho oxidation dye precursor, or (ii) a para oxidation dye precursor, or (iii) a mixture of (i) and (ii), and (iv) at least one 2-sulfurated metaphenylenediamine of the formula ##STR22## wherein Z represents C₁ -C₁₈ alkyl, aralkyl wherein the alkyl moiety is C₁ -C₆, C₁ -C₆ monohydroxyalkyl, C₂ -C₆ polyhydroxyalkyl, aryl or aminoalkyl of the formula ##STR23## wherein n is an integer ranging from 1 to 6, and R₄ and R₅, each independently, represent hydrogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl or C₁ -C₆ acyl, R₁ and R₂, each independently, represent hydrogen, C₁ -C₆ alkyl, C₁ -C₆ monohydroxyalkyl, C₂ -C₆ polyhydroxyalkyl, C₁ -C₆ monocarbamoylalkyl, C₁ -C₆ dialkylcarbamoyl, C₁ -C₆ aminoalkyl, C₁ -C₆ acyl, C₂ -C₆ carbalkoxy, carbamoyl or C₁ -C₆ monoalkylcarbamoyl, R₃ represents hydrogen, C₁ -C₄ alkyl, a nitrile radical, an amide radical, a C₁ -C₄ fluoroalkyl radical, --COOR wherein R represents hydrogen or C₁ -C₄ alkyl, and the acid salts thereof, in the presence of an oxidizing agent.
 12. The oxidation process of claim 11 comprising admixing, at the time of applying said composition to said fibers, a solution of said oxidizing agent in an amount effective to develop a color on said fibers with said composition comprising components (i) or (ii) or (iii) and (iv), the said composition having a pH ranging from 3 to
 11. 13. The oxidation dyeing process of claim 11 comprising a first and second stage operation, said first stage comprising applying to said keratinous fibers an oxidation dye precursor (i), (ii) or (iii) and, said second stage comprising applying to keratinous fibers a composition comprising said 2-sulfurated metaphenylenediamine of formula (I) and thereafter developing a color on said keratinous fibers by applying to said keratinous fibers an oxidizing agent.
 14. The oxidation dyeing process of claim 13 wherein said oxidizing agent is applied to said keratinous fibers in said second stage.
 15. The oxidation dyeing process of claim 13 wherein said oxidizing agent is applied to said keratinous fibers in a third stage.
 16. The oxidation dyeing process of claim 11 wherein said composition is applied to said keratinous fibers for a period ranging from 10 to 40 minutes and thereafter said keratinous fibers are rinsed, washed with shampoo, rinsed and dried. 